Tall oil metal compound and process of making same



flour, asbestos, clay,

be dissolved in benzene, petroleum distillate, etc,

, Patented Dec. 22; 1942 TALL on. METAL COMPOUND or MAKING PROCESS SAME Harry Bun-ell, Newark," N. J., assignor to Ellis- Foster Company, a corporation of New Jersey Serial No. 309,701

No Drawing. upputatidii December 16, 1939,

1 Claim. (Cl. 260-375) This invention relates to plastic products derived from the by-product of wood pulp manufacture known as tall oil.

Tall oil is a dark brown, odorous, viscous liquid usually containing some suspended solid matter; it is of varied composition depending onthe raw wood from which it is derived and on the exact pulping procedure. It is obtained from the black liquor of wood pulping processes and consists chiefly of resin acids, fatty acids, and unsaponifiable material (stated to be sterols).

I have found that this-cheap, abundantly available material may' be converted into plastic masses capable of hardening by heating, and which thus has utility in the wide field of allied plastic arts., Among the products which may be made from the tall oil material are coatings such as paints for concrete, road binding agents, roofing compounds, floor or wall tile, electrical insu lation, rubber compounding materials, molding compositions particularly those for cold moldmg, linoleum, sheeting compounds, impregnated cloth, etc. The plastic may be combined with otheringredients, for instance fillers such as wood mica, and the like, orit may in the manner well known to the art.

The tall oil plastic is prepared by reacting the tall oil at elevated temperatures with metallic compounds, preferably compounds of heavy metals or alkaline earth metals. Oxides, hydroxides, chlorides, acetates, or carbonates are con' venient compounds of the metals, and any metal may be used except those of group I in the periodic table. There are economic limitations which make it desirable to use such readily available compounds as white lead, red lead, litharge, lead peroxide, manganese dioxide, calcium oxide, fer no oxide, ferric carbonate, aluminum acetate,

- magnesium hydroxide, or calcium chloride.

The ratio of metal compound to be combined with the tall oil must be above a critical minimum. In order that this limitation may be expressed, it is convenient to consider the tall oil as a single monocarboxylic acid of molecular heavy. metal or alkaline earth metal (in compound form) regardless ofthe valence of the metal. Since the-metals of these classes exist in a condition wherein the valence is greater than one this means that soaps of tall oil, which are, of course, known to the prior art, are not the reaction products resulting from the process of this invention. Soaps would be formed by'reacting one equivalent of a metal (i. e. one atomic weight divided by the valence) with one equivalent of tall oil. Without exception among those metals tried, the soaps of tall oil were soft, sticky. gummy masses unsuited for the present purposes, whereas the adducts of at least one atomic weight of metal with one equivalent of tall oil were solids possessing highly desirable properties. As a general statement it may be said that the proportion of metallic compound necessary to use for each equivalent weight of tall oil is themolecular weight (M) of the compound divided by the number of atoms (a). of metal per molecule of the compound: that is, it is M/a. This amount is illustrated in the following, wherein is given the minimum amount (M/a) of various metallic compounds required to form the hereindescribed products when combined with one equivalent of tall oil:

The exact nature of the tall oil-metal adducts has not been investigated but it may readily be seen that they are novel and utilitarian products.

, The mode of formation of the tall oil plastics consistsof heating an intimate mixture of tall weight determined by the acid number, with the understanding that such a consideration is for purposes of computation only and does not represent the true nature of the tall oil. -Hereinafter the expression one equivalent of tall oil is to be construed to mean that amount of tall oil equivalent to one atomic weight of hydrogen ion, as determined by the acid number. For example, if the acid number of a sample of tall oil is 168, this means that the average molecular weight of the material counted-as monobasic acid oil or similar material and metal compound to an elevated temperature preferably not over 300 C. and conveniently at or less than 250 0.

Heating should be continued long enough to form a product which is solid at room temperature and this ordinarily occurs in 15 minutes or less at 250 C. and frequently it is necessary only to heat the mixture up to this temperature. Lower temperatures require longer heating times but produce similar results. In certain cases it is desirable only to Partially react the constituents is about 330. Considering the ingredients in this 7 light, it may be stated that it is necessary in the present invention to react one equivalent of tall oil with at least one atomic weight of the at one stage and to complete the conversion in a later stage. Variations of the mode of heating are illustrated in the examples.

Part of the metal may be combined with the tal1. oil at lower temperatures if desired, for instance'by the well known methods of soap formation, and then sufllclent additional metal compound may be later reacted at elevated temperatures: combinations of two or more metals may be used.

Various modifications of the invention will occur to those skilled in the art, and the follow-,

ing examples are illustrative onlyand should not be construed so as to limit the scope or proportions beyond the limits already described.

The ingredients were thoroughly mixed and partiallyreacted together by subjecting them to the action of a steam heated Banbury for 15 minutes. The product, which contained 15% tall oil, was a stiff plastic mass, substantially solid to the touch at room temperature. It remained sufliciently plastic, however. to form an excellentcold molding composition.

The granulated product was cold molded at 10 tons per square inch. .The moldings were smooth surfaced, rigid and had excellent handling properties. They werebaked in an oven at 80 C. for 16 hours, followed by hours at 150 C.

The finished products were well formed, smooth; non-blistered, very hard, dense, strong, odorless moldings of light brown color. They showed an impact strength which was 44% higher than that possessed by a cold-molded piece made with the same proportion of a conventional binder consisting of gilsonite, stearin pitch and drying oil.

EXAMPLE 2 Parts .Tall oil (acid number 181) 60 White lead. (2PbCO3-Pb(QH)2) 55 Powdered mineral filler 142 Asbestos floats 143 The ingredients were subjected to the action of a steam-heated Banbury mixer for 15 minutes. The product was a rather hard, but plastic mass which could be cold molded at tons per square inch pressure to form easilyhandled molded pieces. I

The moldings were baked according to the following heating schedule:

Hours heated Temperature eal- KOO: I I I The baked moldings were light grayish-brown colored, very hard and dense, substantially odorless, and strong.

The ingredients were treated by the procedure of Example 2, including the same baking schedule. The molded articles were black and very hard, dense, and strong.

EXAMPLE 4 Parts Tall oil (acid number 181) 80 Red lead (Pbzoil 65 Powdered mica schist Asbestos floats 260 were thoroughly mixed and mixing for 25 minutes in a which was heated by circu- The ingredients partly reacted by Banbury machine lating steam through the jacket and rotors. The

then sheeted by passrolls. The resulting stiff, hot, plastic mass was ing between heated steel sheet was cured by baking for 24 hours at temperature slowly rising to 150 C. The product could be cut into geometrical shapes to serve as a brick red, glossy, hard floor tile. I

EXAMPLE 5 Parts Tall oil (acid number 181) 120 Red lead (PbaOs) 97 The ingredients were stirred together and heated in an open vessel to 150 C, The viscous mass was cooled to 90 C. and spread on heavy canvas duck. The plastic was worked into the cloth by repeatedly passing through heated rolls, and then baked at 90 C. until tack-free. The prod not was a tough, waterproof, leather like sheet.

EXAMPLE 6 Parts Tall oil (acidnumber 161) Red iron oxide 40 Red lead- 10 Asbestos floats 50 Groundmineral filler 200 The ingredients were mixed and partially reacted for 8 minutes in Banbury heated to 195 C. The product was cold molded at 7500 pounds per square inch. The flow was excellent,

V The moldings were baked at 150 C. for 16 hours;

they were hard even when hot, the color was brick red, and the strength fair.

EXAMPLE '7 Parts Tall oil (acid number 161).....' 50 White lead 1. 50 Cobalt oxide 1 Wood flour The ingredients were mixed and reacted together for 1 hour. in a Banbury heated to 195 C. The cold molded at 5000 pounds per square inch, the moldings being firm and altogether handleable. They were baked at C. for 16 hours followed by 10 hours at C. The

finished. articles were dark brown, hard, un-

blistered, odorless, and strong.

Exmurtr: 8

' Parts Ground cork 50 Tall oil 50 White lead -L 50 Cobalt oxide 1 The ingredients were milled and reacted together for 30 minutes in the Banbury mixer which was heated at 1'70-195 C. The hot mixture, which was soft and rubbery, was pressed into a large shallow tray to form a layer about one quarter inch thick. The layer was held under pressure of about 50 pounds per square inch for 15 minutes while cooling. Theproduct was an elastic, resilient, tough, well bound, linoleum-like mathe moldings being slightly plastic but readily handleable.

. zene by heating. The

terial of dark brown color and very slight odor.

The-surface had a slight initial tack which dis- EXAMPLE 9 Parts Tall oil (acid number 161) 50 White lead 50 Cobalt oxide 1 The ingredients were mixed together and heated up to 250 C. Extensive foaming occurred in the initial stages of reaction, and the material became more viscous with continued heating. The resin was poured into a shallow pan and it hardened to a dark gray, brittle solid.

The resinous material was dissolved in 80 parts Varsol (petroleum distillate) and 88 parts benviscosity of the solution was reduced by adding 10 parts ethanol. The spirit varnish was painted on a test strip of concrete flooring. The coating dried in 5 minutes to a slightly tacky film which was perfectly dry and odorless after 24 hour After 2 months the coating showed very little wear .in spite of heavy pedestrian traflic. The coating wasv also an effective dust layer.

EXAMPTJ: I Part4 Parts 'I'all oil (one equivalent) 20 Pba04 (0.168 mol, or 0.503 atomic equivalent) 6.6

The ingredients were mixed together and heated in an open vessel. When 180 C. was reached the color changed from red to dark brownand progressively darkened a creased to 250 C. The melt showed no increase in viscosity and remained liquid after heating for 2 hours at 250 C. The cooled product was a black, soft, tacky mass of no value for the pur- I V 3 Part 3 uses a somewhat increased amount of red lead (2 .moles tall oil to about 1% atomic weights of lead) but without much change in the physical properties of the product. Part C uses the proportion of about 2 moles tall oil to 2 atomic weights of lead and shows distinctly the unexpected results obtained when 1 equivalent of tall oil is reacted with at least 1 atomic weight of a metal.

The ingredients were heated together to 130 0.,

when foaming had almost ceased. 100' parts water and 100 parts ethanol were then added. 9.5 parts PbAcz-3Hz0, dissolved in 200 parts water were added to the sodium soap solution, a gummy lead soap precipitating. This was thoroughly washed with water and heated to 250 C. The

- cooled product was soft and tacky, strongly re-' heating this soap with an extra amount of a metal compound a new product is obtained.

Examnn 12 I Parts Tall oil (acid number 101) 150 Red lea' 150 s the temperaturewas in- 40 poses herein contemplated.

PartB- Parts Tall 011 (one equivalent) 20 Red lead (0.255 mol or 0.768 atomic equivalent) 10 The ingredients were heated as in part A. The same behavior was noted and the product was apparently identical.

' Part0 I Parts Tall oil (one equivalent) 20 R'ed lead (0.356 mole or 1.06 atomic equivalents) 14 The ingredients were mixed and heated together in an open vessel. At 110 C. 'considerable-foaming occurred. At 180 C. a very slight darkening occurred but the distinctive red color'persisted and did not darken as heating progressed. At' 230 C. there'was a rapid increase in viscosity and the temperature dropped to 210 Q. As heating was continuedto 250 C. a. soft, stringy. unstirrable gel quickly formed which-would not remelt. The experiments immediately above indicate the minimum of metal compound required for the tall oil products of the present invention. Part alent of tall 011, and the physical condition of the product.

Compound Mols Physical condition of cooled product PbO 0. 50 Soft and tacky. PbO; 1. 00 Hard and brrttle.

0. 50 Soft, tacky, plastic. PbO, 1.00 Hard, black, brittle, resinous. 2PbCO;-Pb(0H)z;. 0. 272 Tacky semi-solid. 2PbCO;-Pb(0H); 0. 337 Hard, br1ttlc,.non-tacky. PbAcg 0. 50 Soft semi-solid.

PbAOg- ,1. 00 Hard, black resinous. MnAci-4H1O 0. 50 Soft semi-solid. MHACrQHfl L l. 00 Hard, black, brittle, friable. Mums-4H; 3. 00. Brown, hard, strong. MnO, 1. 01 Slightly soft, tacky, black. Mn0 2. 62 Dark brown, hard, brittle, solid. Mp0," 4. 02 Hard, black, resinous. AlAczOH 0.333 Dark brown, soft, plastic. AlAmOH- l. 06 Brown, opaque, hard, brittle. AlAc DH. 1. 89 Translucent. brittle, hard. CaO 0. 50 Liquid with white precipitate. CaO 1. 00 Light brown, friable solid. Mg(OH) 4. 01 Black, brittle, fragile solid.

Auses lead in proportion sumcient to form a soap. That is, tall oil is reacted with 1 chemical equivalent of lead (2 moles tall oil to 1 atomic weight of lead) .to yield a soft, black, stickymass.

parts A and B of Ex- In the above example an ordinary lead scan of tall oil was prepared and characterized. By

The ingredients were heated together in an open vessel up to 263 0. when gelation started. Heating wasstopped and gelation spontaneously continued until a solid rubbery mass was obtained. 260 parts of this product were then milled on differential rolls with 26 g. gum rubber. The

1 product was a brick red, stiflly plastic mass which possessed rubbery or elastic properties, and was very flexible in thin layers.

Exam/mar: 13

j A large variety of compounds in addition to those of the preceding examples was reacted with tall oil according to the method of Example 10,

parts .A to C. The following table lists the compounds, the number of mols used for each equiv- From the examples it is evident that the reaction between an equivalent of tall oil and one atomic equivalent of a metal to yield solid, alkaliresistant, technically useful products of high soltening point is quite a general one. -Naturally, characteristic difierences will occur in the products depending on the source of tall oil and the metal compound used. Certin minor anomalies which may be mentioned are the facts that some oxides such as M1102 or F8203 react more slowly than other oxides or other compounds of the same metals; consequently it is advisable to increase the proportion of such metals to more than one atomic equivalent per equivalent of tall oil. When such addition is made it may be found in certain instances (notably with MnOz, PbOz and PhD) that the hot adduct is less viscous or more mobile than a similar product resulting from the use of less of the metal compound; however, the cooled products are harder 3 when more metal compound is used. Some compounds such as A1203 or A1(OH)a-xH2O react so slowly with tall oil as to limit their usefulness. Tall oil adducts of such metals may be formed, however, by altering the anion constituent, and

the acetate will frequently be found useful. Ex-

cessive heating of some adducts such as the calcium or antimony products is to be avoided .as they are subject to decomposition, but generally the adducts are very stable.

What I claim is:

The reaction product of one equivalent weight of tall oil with at least one-third mole of red lead.

HARRY BURRELL. 

